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Chapter 13: Chemical Equilibria

Chapter 13: Chemical Equilibria. Dr. Aimée Tomlinson. Chem 1212. Section 13.1. Equilibrium State. Graphical Representation. After some time: [N 2 O 4 ] stops increasing [NO 2 ] stops decreasing Solution from brown to clear and back again Rate_forward = rate_reverse.

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Chapter 13: Chemical Equilibria

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  1. Chapter 13: Chemical Equilibria Dr. Aimée Tomlinson Chem 1212

  2. Section 13.1 Equilibrium State

  3. Graphical Representation After some time: [N2O4] stops increasing [NO2] stops decreasing Solution from brown to clear and back again Rate_forward = rate_reverse After some time: [N2O4] stops decreasing [NO2] stops increasing Solution from clear to brown and back again Rate_forward = rate_reverse

  4. Chemical Equilibrium Defn: a phenomenon in which the concentrations of reactants and products remain constant over time NOTE: this does not mean the concentrations go to zero!

  5. Section 13.2 The Equilibrium Constant, Kc

  6. Equilibrium Constant Expression AKA Law of Mass Action: the chemical equilibrium expression will give rise to a characteristic value for a given temperature For the General case: Kc is the equilibrium constant in terms of concentrations

  7. Example Recall: Write the Kc for both the forward and reverse directions for the following:

  8. Mass Action Rule #1 Kc in the forward direction is the inverse for the reverse direction

  9. Section 13.3 Equilibrium Constant, Kp

  10. Generalized Kp Example: What is Kc and Kp for the reaction below.

  11. Numeric Example A reaction vessel contains an eq mix of the following: PSO2 = 0.0018 atm, PO2 = 0.0032 atm, and PSO3 = 0.0166 atm. What is the eq constant for the following reaction?

  12. How are Kp & Kc Related? We start with the ideal gas Law: Next, we plug into the Kc expression Using Previous Example:

  13. Kp & Kc Generalized Relationship Where n = moles(g)products - moles(g)reactants For previous example we had: So n = 3-2 = 1 hence Kp = KcRT

  14. Another Example For which of the following will Kp = Kc? So only 2.) & 3.) will work.

  15. One More Example What is the Kp of the reaction below at 325C given Kc = 5.0?

  16. Section 13.4 Heterogeneous Equilibrium

  17. The Two Types of Equilibria Heterogeneous when the reactants/products are in more than one phase Homogeneous when the reactants/products are all in the same phase

  18. For Eq we never include: Solids Pure Liquids

  19. Handling Combined Equations

  20. Mass Action Rule #2 When adding up equilibrium equations to get an overall the product of their equilibrium constants will give rise to the Kc of the overall equation

  21. Example Problem Calculate the Kc for Using the data below:

  22. How does factor multiplication impact Kc?

  23. Mass Action Rule #3 Multiplying a chemical by a factor leads to exponential factor for the Kc

  24. Summary of Mass Action Rules

  25. Example Problem If Kc = 2.4 x 10-3 for what is it for the following?

  26. Section 13.5 Using the Equilibrium Constant

  27. Judging the Extent of Reaction • Kc > 103 products predominate over reactants: • reaction proceeds nearly to completion • very little reactant is left • Kc< 10‾3 reactants predominate over products: • reaction hardly proceeds at all • very little product is produced • 10‾3< Kc < 103 neither dominates both are present at eq

  28. Reaction Quotient Q Q looks just like Kc but it not guaranteed to be at eq

  29. Using Q for Direction Prediction At Eq we go in neither direction • Need to consume products • Go reverse • To the left • Toward reactants • Need to consume reactants • Go forward • To the right • Toward products

  30. Example – Practice with Q Given the data below is the reaction in equilibrium and if not in which direction will need to go in order to reach eq?

  31. Finding Equilibrium Concentrations We use the "ICE" table: "I"nitial "C"hange "E"q

  32. ICE Example I The value of Kc = 0.0900 at 298K for the reaction below, determine the eq concentrations if initially [H2O] = 0.00432 M and [Cl2O] = 0.00442 M.

  33. ICE Example II The value of Kc for the thermal decomposition of hydrogen sulfide is 2.2 x 10-6 at 1400K. A sample of gas in which [H2S] = 0.600M is heated to 1400K in a sealed vessel. After chemical eq has been achieved, what is the value of [H2S]? Assume no H2 and S2 was present in the original sample.

  34. ICE Example III What are the eq concentrations of each of the species in the following reaction, given the Kc = 5.1 at 700K and the initial concentration of all species is 0.050 M?

  35. Section 13.6-13.9 Le Châtelier’s Principle

  36. Le Châtelier’s Principle • Defn: when a stressor is applied to a system at equilibrium, the system will adjust to counteract the stressor in order to reestablish equilibrium • Stressors include: • Adding or removing reactants or products • Changing the pressure or the volume • Changing the temperature

  37. Stressor I: Concentration Changes • Increase in A or decrease in B: • We will need to consume A (or produce B) to get back to eq • We go: • Forward • Toward product • To the right • Increase in B or decrease in A: • We will need to consume A (or produce B) to get back to eq • We go: • Reverse • Toward reactant • To the left

  38. Stressor II: P or V Changes • Decrease V or increase P: • We increase the number of collisions between molecules • P will increase and V will decrease • Number of moles appears to increase • We go: • Forward • Toward product • To the right • Increase in V or decrease in P: • We decrease the number of collisions between molecules • P will decrease and V will increase • Number of moles appears to decrease • We go: • Reverse • Toward reactant • To the left

  39. LCP Example I For each scenario predict the direction the reaction goes to attain eq: a.) CO is added b.) CH3OH is added c.) Pressure is reduced d.) Volume is increased

  40. Stressor III: Temperature Changes • Unique since this stressor will also change the value for Kc • For exothermic reaction, heat is a product • Reactants → Products + ΔH • Removal of heat will force the reaction to go: • Forward • Toward product • To the right • Addition of heat will force the reaction to go: • Reverse • Toward reactant • To the left • For endothermic reaction, heat is a reactant • ΔH + Reactants → Products • Addition of heat will force the reaction to go: • Forward • Toward product • To the right • Removal of heat will force the reaction to go: • Reverse • Toward reactant • To the left

  41. LCP Example II In what direction will the eq shift when each of the following changes are made to the system at eq? a.) N2O4 is added b.) NO2 is removed c.) Pressure is increased by adding N2 d.) Volume is decreased e.) Temperature is decreased

  42. Section 13.10 Catalytic Effect on Eq There really isn’t one

  43. Section 13.11 Chemical Eq & Kinetics

  44. Another Gen Chem Lie

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